EP0814904A1 - Catalyst for organic compounds in a gas mixture - Google Patents

Catalyst for organic compounds in a gas mixture

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Publication number
EP0814904A1
EP0814904A1 EP96905708A EP96905708A EP0814904A1 EP 0814904 A1 EP0814904 A1 EP 0814904A1 EP 96905708 A EP96905708 A EP 96905708A EP 96905708 A EP96905708 A EP 96905708A EP 0814904 A1 EP0814904 A1 EP 0814904A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
titanium dioxide
organic compounds
active component
catalytically active
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96905708A
Other languages
German (de)
French (fr)
Other versions
EP0814904B1 (en
Inventor
Norbert Landgraf
Erich Hums
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
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Filing date
Publication date
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Publication of EP0814904A1 publication Critical patent/EP0814904A1/en
Application granted granted Critical
Publication of EP0814904B1 publication Critical patent/EP0814904B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g

Definitions

  • DE-OS-38 04 722 discloses a method and a catalyst for removing organic compounds from an exhaust gas. With regard to the method, it is disclosed that the exhaust gas with the organic compound and together with oxygen, in particular together with air, within a predetermined temperature range, for example 250 to
  • a selective catalyst is supplied, which converts the organic compound to environmentally compatible reaction products such as carbon dioxide and water vapor.
  • the acid resistance has an advantageous effect especially in the case of dioxin / furan degradation (formation of HC1, HF).
  • a preferred catalyst here is a catalyst consisting of a mixture of oxides.
  • the catalyst considered here consists to a large extent of titanium dioxide, preferably in the crystalline form of the anatase type.
  • As catalytically particularly active components compounds and / or oxides and / or mixed oxides of the transition All chrome, manganese, cobalt, nickel, copper, vanadium, zinc, molybdenum and tungsten, but preferably also chromium oxide, are added.
  • a catalyst for the oxidation of ammonia is known from EP 0 290 947 B1.
  • This catalyst also consists to a considerable extent of up to 50% by weight of titanium dioxide, which should preferably be present in the crystalline modification of the anatase.
  • the anatase modification usually has a higher BET surface area than the rutile modification.
  • Such a catalyst has a high catalytic activity due to the high BET surface area.
  • DE 38 04 722 A1 or EP 0 290 947 B1 discloses a process for producing such a catalyst for the degradation of organic compounds.
  • titanium dioxide is ground with the active components, mixed intimately and filtered.
  • a binder is added to the resulting filter cake, the resulting mass is mixed and brought into a predetermined form, e.g. applied to plates or extruded in honeycombs or pellets.
  • the molded mass is then dried and subjected to a heat treatment or calcination.
  • the reaction carried out with such a catalyst is exothermic, which is why the reaction can lead to local overheating, so-called hot spots, in the catalyst.
  • the catalyst consists predominantly of titanium dioxide of the anatase type, the specific catalyst surface is irreversibly reduced due to these local overheating, because titanium dioxide of the anatase type is converted into the rutile type by changing the grain size. This has the consequence that the activity of the catalyst deteriorates with increasing operating time.
  • titanium dioxide as a catalyst base material
  • aluminum oxide As an alternative to titanium dioxide as a catalyst base material, it is also known to assemble a catalyst based on aluminum oxide. Such an aluminum oxide-containing catalyst is only slightly susceptible to temperature loads, in particular to local overheating. When using such a catalyst, however, it has been shown that, unlike titanium dioxide catalysts with the customary anatase modification, the catalyst does not have sufficient acid resistance, particularly when halogenated hydrocarbons are broken down.
  • the invention is therefore based on the object of specifying a particularly temperature-stable and acid-resistant catalyst for converting organic compounds contained in a gas mixture.
  • This object is achieved according to the invention with a catalyst of the type mentioned at the outset in that titanium oxide is predominantly present as titanium dioxide of the rutile type with a BET surface area greater than 40 m 2 / g.
  • titanium dioxide as the catalyst base material achieves a particularly good acid resistance of the catalyst, which exceeds the acid resistance of a catalyst with titanium dioxide in the anatase modification as the catalyst base material.
  • the use of titanium dioxide of the rutile type which, in comparison to titanium dioxide of the anatase type, is subject to no or only very slight grain growth at high temperatures, also results in a particularly high temperature stability.
  • the temperature stability is due to the fact that titanium dioxide of the rutile type itself Temperature peaks in the range from 700 to 1000 ° C. show practically no grain size growth which would lead to a decrease in the specific surface area, as is the case with titanium dioxide of the anatase type.
  • titanium dioxide of the rutile type is all the more remarkable because a person skilled in the art conventionally excludes the use of titanium dioxide of the rutile type, since titanium dioxide is usually only used in the rutile modification for the production of white pigments and is therefore usually only available with a relatively small specific surface area of about 10 m 2 / g.
  • titanium dioxide of the anatase type is also commercially available with a relatively high specific surface area of 100 m 2 / g.
  • the proportion of titanium dioxide TiO 2 of the anatase type is less than 25% by weight, based on the total weight of the titanium dioxide used.
  • the catalytic activity of the catalyst becomes particularly great if a compound or several compounds of the elements molybdenum, tungsten, vanadium, copper, iron, chromium and manganese is or are provided as the catalytically active component. Copper manganese spinels, copper chromites, chromium oxides, manganese chromites and iron oxide with vanadium pentoxide are particularly suitable here.
  • the catalyst should not contain any proportion of the catalytically active component. It is advantageous if the proportion of the catalytically active component does not exceed 20% by weight and is preferably between 2 and 10% by weight.
  • the catalyst is particularly practical to use when it is in honeycomb form or in pellet and / or granule form.
  • a catalyst according to the invention can be produced by the process mentioned at the outset under the same conditions which are also customary for producing a catalyst known from the prior art for removing organic compounds from exhaust gases.
  • Titanium dioxide gradually and irreversibly accelerates when the temperature rises from the anatase modification to the rutile modification. When the temperature rises, however, there is no change in the grain size of the rutile. Therefore, it can be assumed that the catalyst has the same or a higher ratio of titanium dioxide in the
  • Rutile modification to titanium dioxide in the anatase modification has like the starting material added at the beginning.
  • Titanium dioxide in the rutile modification with a BET surface area greater than 40 m 2 / g can be produced by largely the same methods known for the rutile made for white pigments with a BET surface area of about 10 m 2 / g is. Such processes are, for example, precipitation from titanium sulfate or oxidic combustion of titanium tetrachloride. If necessary, the crystallization rate must be changed accordingly in order to achieve suitable grain sizes.
  • the exhaust air line 2, shown in FIG. 1, of an industrial plant has an inserted catalyst 6 in the area of an expansion 4.
  • a heat exchanger 10 and a mixing insert 12 are provided in the widening 4 in the flow direction of the exhaust air 8 upstream of the catalytic converter 6.
  • a further heat exchanger 14 is provided in the area of the widening 4, which can be configured with the heat exchanger 10 as a recuperative heat exchanger, as is indicated by the broken lines.
  • a separator for acidic reaction products such as e.g. HC1, HF, may be required.
  • the exhaust air 8 flowing in the exhaust air line 2 is loaded with organic compounds. These include alcohols, solvents, toluene and xylene. Before entering widening 4, the exhaust air has a temperature of approximately 20 ° C., an otherwise conventional air composition and a volume flow of approximately 10,000 Nm 3 / h.
  • the catalyst 6 consists of ceramic honeycomb bodies 16, as is shown in FIG. 2.
  • a honeycomb body 16 usually has a number of cells of 25 to 500 cells / inch 2 .
  • the honeycomb body 16 consists of approximately 90% by weight of titanium dioxide, the titanium dioxide consisting of approximately 95% by weight of the rutile type and approximately 5% of the anatase type.
  • the honeycomb body 16 further contains about 3% by weight of fiber material, for example Glass fibers or fibers made of aluminum oxide and / or silicon oxide, to increase the mechanical strength.
  • the remaining seven% by weight of the catalyst 6 essentially represent the catalytically active substances of the catalyst 6. These are two% by weight of iron oxide F ⁇ 2 ⁇ 3, two
  • the exhaust air 8 is increased to approximately 200 by means of the heat exchanger 10
  • the exhaust air 8 is mixed by means of the mixing insert 12 located downstream of the heat exchanger 10, with the result that there is a homogeneous distribution of the temperature of the exhaust air 8 over the entire cross section of the expansion 4.
  • these compounds become largely environmentally compatible substances, e.g. B. carbon dioxide and water.
  • the exhaust air emerging from the catalyst 6 is free of harmful organic compounds if the catalyst 6 is dimensioned accordingly.
  • the volume of the catalyst 6 should be selected such that the volume flow of the exhaust air 8 passed through it in one hour does not exceed its volume by a factor of 50,000, i.e. a maximum of 50,000 per hour for the exhaust airspeed.
  • the exhaust air velocity should preferably be between 500 and 10,000 per hour.
  • the heat previously supplied by means of the heat exchanger 10 is extracted from the exhaust air 8 again. This heat can be returned to the heat exchanger 10 become.
  • the exhaust air line 2 can be routed via the heat exchanger 10 after it has left the catalyst 6, if the latter is designed as a recuperative heat exchanger.
  • the catalyst 6 Due to the selection of titanium dioxide of the rutile type with a specific surface area, also called BET surface area, greater than 80 m 2 / g, the catalyst 6 achieves a particularly high acid resistance, temperature stability and catalytic activity.
  • the acid stability is further increased by using titanium dioxide of the rutile type; the temperature stability is achieved by the high proportion of titanium dioxide of the rutile type.
  • the high catalytic activity is achieved on the one hand by the choice of the BET surface area greater than 40 m 2 / g and on the other hand by the choice of the catalytically active components.
  • FIG. 2 shows alternative shaped catalyst bodies 18 and 20. These are catalyst granules 18 and catalyst pellets 20.
  • the catalyst granules 18 can consist, for example, of beads with a diameter of approximately 1 to 5 mm.
  • the pellets 20 usually have a diameter of approximately 1 to 5 mm and a length of approximately 5 to 30 mm.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The catalyst concerns a catalyst for organic compounds, such as hydrocarbons, halogenated hydrocarbons, alcohols and solvents, in a gas mixture. In order to make the catalyst particularly stable to the action of heat and acids, the invention calls for the catalyst (6, 16, 18, 20) to include titanium oxide and at least one catalytically active component. The titanium oxide is present mainly in the form of rutile titanium dioxide (TiO2) with a BET surface area greater than 40 m2/g. The catalyst can be used to clean any kind of combustion gases and to clean industrial exhaust air.

Description

Beschreibungdescription
Katalysator zur Umsetzung von in einem Gasgemisch enthaltenen organischen VerbindungenCatalyst for converting organic compounds contained in a gas mixture
Die Erfindung bezieht sich auf einen Katalysator zur Umset¬ zung von in einem Gasgemisch enthaltenen organischen Verbin¬ dungen, umfassend Titanoxid und mindestens eine weitere kata¬ lytisch aktive Komponente. Unter organischen Verbindungen werden hierbei im allgemeinen Kohlenwasserstoffe, Lösungsmit¬ tel, Kohlenmonoxid, zyklische und aromatische Verbindungen sowie halogenierte Kohlenwasserstoffe, insbesondere Dioxine und Furane, verstanden. Solche Gasgemische können beispiels¬ weise Automobilabgase, Industrieabluft, Abgase von stationä- ren Verbrennungsmotoren und Rauchgase von Verbrennungsanla¬ gen, wie z. B. Kraftwerke und Müllverbrennungsanlagen, sein.The invention relates to a catalyst for the conversion of organic compounds contained in a gas mixture, comprising titanium oxide and at least one further catalytically active component. Organic compounds are generally understood to mean hydrocarbons, solvents, carbon monoxide, cyclic and aromatic compounds and halogenated hydrocarbons, in particular dioxins and furans. Such gas mixtures can, for example, automobile exhaust gases, industrial exhaust air, exhaust gases from stationary internal combustion engines and flue gases from combustion plants, such as, for example, B. power plants and waste incineration plants.
Aus der DE-OS-38 04 722 sind ein Verfahren und ein Katalysa¬ tor zur Beseitigung von organischen Verbindungen aus einem Abgas bekannt. Bezüglich des Verfahrens ist es offenbart, daß das Abgas mit der organischen Verbindung und zusammen mit Sauerstoff, insbesondere zusammen mit Luft, innerhalb eines vorgegebenen Temperaturbereichs, beispielsweise 250 bisDE-OS-38 04 722 discloses a method and a catalyst for removing organic compounds from an exhaust gas. With regard to the method, it is disclosed that the exhaust gas with the organic compound and together with oxygen, in particular together with air, within a predetermined temperature range, for example 250 to
500 °C, einem selektiven Katalysator zugeführt wird, der die organische Verbindung zu umweltverträglichen Reaktionsproduk¬ ten, wie Kohlendioxid und Wasserdampf, umsetzt. Die Säurebe¬ ständigkeit wirkt sich gerade beim Dioxin/Furan-Abbau (Bildung von HC1, HF) vorteilhaft aus. Ein hierbei bevorzug¬ ter Katalysator ist ein aus einer Mischung von Oxiden beste- hender Katalysator. Der hier betrachtete Katalysator besteht zu einem großen Gewichtsanteil aus Titandioxid, und zwar be¬ vorzugt in der kristallinen Form des Anatas-Typs. Als kataly¬ tisch besonders aktive Komponenten sind dem Titandioxid Ver¬ bindungen und/oder Oxide und/oder Mischoxide der Obergangsme- talle Chrom, Mangan, Kobalt, Nickel, Kupfer, Vanadium, Zink, Molybdän und Wolfram, bevorzugt aber auch Chromoxid, beigege¬ ben.500 ° C, a selective catalyst is supplied, which converts the organic compound to environmentally compatible reaction products such as carbon dioxide and water vapor. The acid resistance has an advantageous effect especially in the case of dioxin / furan degradation (formation of HC1, HF). A preferred catalyst here is a catalyst consisting of a mixture of oxides. The catalyst considered here consists to a large extent of titanium dioxide, preferably in the crystalline form of the anatase type. As catalytically particularly active components, compounds and / or oxides and / or mixed oxides of the transition All chrome, manganese, cobalt, nickel, copper, vanadium, zinc, molybdenum and tungsten, but preferably also chromium oxide, are added.
Des weiteren ist aus der EP 0 290 947 Bl ein Katalysator zur Oxidation von Ammoniak (NH3) bekannt. Auch dieser Katalysator besteht zu einem erheblichen Gewichtsanteil von bis zu 50 % aus Titandioxid, welches bevorzugt in der kristallinen Modi¬ fikation des Anatas vorliegen sollte. Die Anatas-Modifikation weist nämlich üblicherweise eine höhere BET-Oberfläche als die Rutil-Modi-fikation auf. Ein derartiger Katalysator be¬ sitzt aufgrund der hohen BET-Oberfläche eine große katalyti- sche Aktivität.Furthermore, a catalyst for the oxidation of ammonia (NH 3 ) is known from EP 0 290 947 B1. This catalyst also consists to a considerable extent of up to 50% by weight of titanium dioxide, which should preferably be present in the crystalline modification of the anatase. The anatase modification usually has a higher BET surface area than the rutile modification. Such a catalyst has a high catalytic activity due to the high BET surface area.
Aus der DE 38 04 722 AI oder der EP 0 290 947 Bl ist ein Ver¬ fahren zur Herstellung eines derartigen Katalysators zum Ab¬ bau von organischen Verbindungen bekannt. Dabei wird Titandi¬ oxid mit den aktiven Komponenten gemahlen, innig gemischt und gefiltert. Dem entstehenden Filterkuchen wird ein Bindemittel zugegeben, die entstehende Masse vermischt und in eine vorge¬ gebene Form gebracht, z.B. auf Platten aufgetragen oder in Waben oder Pellets extrudiert. Anschließend wird die geformte Masse getrocknet und einer Wärmebehandlung unterzogen bzw. calciniert.DE 38 04 722 A1 or EP 0 290 947 B1 discloses a process for producing such a catalyst for the degradation of organic compounds. In this case, titanium dioxide is ground with the active components, mixed intimately and filtered. A binder is added to the resulting filter cake, the resulting mass is mixed and brought into a predetermined form, e.g. applied to plates or extruded in honeycombs or pellets. The molded mass is then dried and subjected to a heat treatment or calcination.
Die mit einem derartigen Katalysator durchgeführte Reaktion ist exotherm, deshalb kann es durch die Reaktion zu örtlichen Oberhitzungen, sogenannten hot spots, bei dem Katalysator kommen. Weil der Katalysator überwiegend aus Titandioxid des Anatas-Typs besteht, verringert sich bedingt durch diese ört¬ lichen Oberhitzungen die spezifische Katalysatoroberfläche irreversibel, weil Titandioxid des Anatas-Typs unter Verände¬ rung der Korngröße in den Rutil-Typ umgewandelt wird. Dies hat zur Folge, daß sich die Aktivität des Katalysators mit zunehmender Betriebsdauer verschlechtert.The reaction carried out with such a catalyst is exothermic, which is why the reaction can lead to local overheating, so-called hot spots, in the catalyst. Because the catalyst consists predominantly of titanium dioxide of the anatase type, the specific catalyst surface is irreversibly reduced due to these local overheating, because titanium dioxide of the anatase type is converted into the rutile type by changing the grain size. This has the consequence that the activity of the catalyst deteriorates with increasing operating time.
Alternativ zu Titandioxid als Katalysatorgrundstoff ist es auch bekannt, einen Katalysator auf der Basis von Aluminiu¬ moxid zusammenzusetzen. Ein solcher aluminiumoxidhaltiger Ka¬ talysator ist nur wenig anfällig für Temperaturbelastungen, insbesondere für örtliche Oberhitzungen. Beim Einsatz eines solchen Katalysators hat es sich jedoch gezeigt, daß der Ka- talysator im Gegensatz zu Titandioxid-Katalysatoren mit der gebräuchlichen Anatas-Modifikation keine ausreichende Säure¬ beständigkeit, insbesondere beim Abbau halogenierter Kohlen¬ wasserstoffe, besitzt.As an alternative to titanium dioxide as a catalyst base material, it is also known to assemble a catalyst based on aluminum oxide. Such an aluminum oxide-containing catalyst is only slightly susceptible to temperature loads, in particular to local overheating. When using such a catalyst, however, it has been shown that, unlike titanium dioxide catalysts with the customary anatase modification, the catalyst does not have sufficient acid resistance, particularly when halogenated hydrocarbons are broken down.
Der Erfindung liegt daher die Aufgabe zugrunde, einen beson¬ ders temperaturstabilen und säurebeständigen Katalysator zur Umsetzung von in einem Gasgemisch enthaltenen organischen Verbindungen anzugeben.The invention is therefore based on the object of specifying a particularly temperature-stable and acid-resistant catalyst for converting organic compounds contained in a gas mixture.
Diese Aufgabe wird mit einem Katalysator der eingangs genann¬ ten Art erfindungsgemäß dadurch gelöst, daß Titanoxid über¬ wiegend als Titandioxid des Rutil-Typs mit einer BET- Oberfläche größer 40 m^/g vorliegt.This object is achieved according to the invention with a catalyst of the type mentioned at the outset in that titanium oxide is predominantly present as titanium dioxide of the rutile type with a BET surface area greater than 40 m 2 / g.
Durch die Verwendung von Titandioxid als Katalysatorgrund¬ stoff wird eine besonders gute Säurebeständigkeit des Kataly¬ sators erzielt, die die Säurebeständigkeit eines Katalysators mit Titandioxid in der Anatas-Modifikation als Katalysator¬ grundstoff übertrifft. Durch die Verwendung von Titandioxid des Rutil-Typs, welches im Vergleich zu Titandioxid des Ana¬ tas-Typs bei hohen Temperaturen keinem oder nur sehr geringem Kornwachstum unterliegt, wird auch eine besonders hohe Tempe¬ raturstabilität erzielt. Die Temperaturstabilität ist bedingt durch die Tatsache, daß Titandioxid des Rutil-Typs selbst bei Temperaturspitzen im Bereich von 700 bis 1000 °C so gut wie kein Korngrößenwachstum zeigt, welches zu einer Abnahme der spezifischen Oberfläche führen würde, wie dies bei Titandi¬ oxid vom Anatas-Typ der Fall ist. Die Verwendung von Titandi- oxid des Rutil-Typs ist um so bemerkenswerter, weil ein Fach¬ mann herkömmlicherweise die Verwendung von Titandioxid des Rutil-Typs ausschließt, da Titandioxid in der Rutil- Modifikation üblicherweise nur für die Herstellung von Wei߬ pigmenten verwendet wird und daher in der Regel nur mit einer relativ geringen spezifischen Oberfläche von etwa 10 m2/g er¬ hältlich ist. Dagegen ist Titandioxid des Anatas-Typs auch mit einer relativ hohen spezifischen Oberfläche von 100 m2/g im Handel verfügbar.The use of titanium dioxide as the catalyst base material achieves a particularly good acid resistance of the catalyst, which exceeds the acid resistance of a catalyst with titanium dioxide in the anatase modification as the catalyst base material. The use of titanium dioxide of the rutile type, which, in comparison to titanium dioxide of the anatase type, is subject to no or only very slight grain growth at high temperatures, also results in a particularly high temperature stability. The temperature stability is due to the fact that titanium dioxide of the rutile type itself Temperature peaks in the range from 700 to 1000 ° C. show practically no grain size growth which would lead to a decrease in the specific surface area, as is the case with titanium dioxide of the anatase type. The use of titanium dioxide of the rutile type is all the more remarkable because a person skilled in the art conventionally excludes the use of titanium dioxide of the rutile type, since titanium dioxide is usually only used in the rutile modification for the production of white pigments and is therefore usually only available with a relatively small specific surface area of about 10 m 2 / g. In contrast, titanium dioxide of the anatase type is also commercially available with a relatively high specific surface area of 100 m 2 / g.
Mit Bezug auf die Temperaturstabilität ist es besonders vor¬ teilhaft, wenn der Anteil an Titandioxid Tiθ2 des Anatas-Typs kleiner 25 Gew.-% ist, bezogen auf das Gesamtgewicht des ein¬ gesetzten Titandioxids.With regard to the temperature stability, it is particularly advantageous if the proportion of titanium dioxide TiO 2 of the anatase type is less than 25% by weight, based on the total weight of the titanium dioxide used.
Die katalytische Aktivität des Katalysators wird besonders groß, wenn als katalytisch aktive Komponente eine Verbindung oder mehrere Verbindungen der Elemente Molybdän, Wolfram, Va¬ nadium, Kupfer, Eisen, Chrom und Mangan vorgesehen ist bzw. sind. Hierbei eignen sich besonders Kupfer-Mangan-Spinelle, Kupferchromite, Chromoxide, Manganchromite und Eisenoxid mit Vanadiumpentoxid.The catalytic activity of the catalyst becomes particularly great if a compound or several compounds of the elements molybdenum, tungsten, vanadium, copper, iron, chromium and manganese is or are provided as the catalytically active component. Copper manganese spinels, copper chromites, chromium oxides, manganese chromites and iron oxide with vanadium pentoxide are particularly suitable here.
Aus Kostengründen und aufgrund technischer Gegebenheiten sollte der Katalysator nicht einen beliebig hohen Anteil der katalytisch aktiven Komponente beinhalten. Es ist vorteil¬ haft, wenn der Anteil der katalytisch aktiven Komponente 20 Gew.-% nicht übersteigt und vorzugsweise zwischen 2 und 10 Gew.-% liegt. Der Katalysator ist besonders praktisch zu handhaben, wenn er in Wabenform oder in Pellet- und/oder Granulatform vorliegt.For reasons of cost and technical conditions, the catalyst should not contain any proportion of the catalytically active component. It is advantageous if the proportion of the catalytically active component does not exceed 20% by weight and is preferably between 2 and 10% by weight. The catalyst is particularly practical to use when it is in honeycomb form or in pellet and / or granule form.
Die Herstellung eines erfindungsgemäßen Katalysators kann prinzipiell nach dem eingangs erwähnten Verfahren unter den¬ selben Bedingungen erfolgen, die auch zur Herstellung eines aus dem Stand der Technik bekannten Katalysators zur Entfer¬ nung von organischen Verbindungen aus Abgasen üblich sind.In principle, a catalyst according to the invention can be produced by the process mentioned at the outset under the same conditions which are also customary for producing a catalyst known from the prior art for removing organic compounds from exhaust gases.
Titandioxid geht allmählich und bei Temperaturerhöhung be¬ schleunigt irreversibel von der Anatas-Modifikation in die Rutil-Modifikation über. Bei einer Temperaturerhöhung findet allerdings keine Veränderung der Korngröße des Rutils statt. Daher kann davon ausgegangen werden, daß der Katalysator das gleiche oder ein höheres Verhältnis von Titandioxid in derTitanium dioxide gradually and irreversibly accelerates when the temperature rises from the anatase modification to the rutile modification. When the temperature rises, however, there is no change in the grain size of the rutile. Therefore, it can be assumed that the catalyst has the same or a higher ratio of titanium dioxide in the
Rutil-Modifikation zu Titandioxid in der Anatas-Modifikation aufweist wie das eingangs zugefügte Ausgangsmaterial.Rutile modification to titanium dioxide in the anatase modification has like the starting material added at the beginning.
Titandioxid in der Rutil-Modifikation mit einer BET-Ober- fläche größer als 40 m2/g kann nach weitgehend denselben Ver¬ fahren hergestellt werden, welche für das für Weißpigmente gefertigte Rutil mit einer BET-Oberfläche von etwa 10 m2/g bekannt ist. Derartige Verfahren sind z.B. Fällung aus Ti- tanylsulfat oder oxidische Verbrennung von Titantetrachlorid. Es muß gegebenenfalls die Kristallisationsgeschwindigkeit entsprechend geändert werden, um geeignete Korngrößen zu er¬ zielen.Titanium dioxide in the rutile modification with a BET surface area greater than 40 m 2 / g can be produced by largely the same methods known for the rutile made for white pigments with a BET surface area of about 10 m 2 / g is. Such processes are, for example, precipitation from titanium sulfate or oxidic combustion of titanium tetrachloride. If necessary, the crystallization rate must be changed accordingly in order to achieve suitable grain sizes.
Ausführungsbeispiele der Erfindung werden anhand einer Zeich- nung näher erläutert. Dabei zeigen:Exemplary embodiments of the invention are explained in more detail with reference to a drawing. Show:
FIG 1 in schematischer Darstellung eine Abluftleitung mit einem Katalysator zur Umsetzung von organischen Ver¬ bindungen; und FIG 2 in schematischer Darstellung mögliche Ausführungsfor¬ men des in Figur 1 verwendeten Katalysators.1 shows a schematic representation of an exhaust air line with a catalyst for converting organic compounds; and 2 shows a schematic representation of possible embodiments of the catalyst used in FIG. 1.
Die in Figur 1 dargestellte Abluftleitung 2 einer hier nicht weiter dargestellten Industrieanlage weist im Bereich einer Aufweitung 4 einen eingesetzten Katalysator 6 auf. In der Aufweitung 4 sind in Strömungsrichtung der Abluft 8 vor dem Katalysator 6 ein Wärmetauscher 10 und ein Mischeinsatz 12 vorgesehen. In Strömungsrichtung der Abluft 8 nach dem Kata- lysator 6 ist im Bereich der Aufweitung 4 ein weiterer Wärme¬ tauscher 14 vorgesehen, der mit dem Wärmetauscher 10 als Re- kuperativ-Wärmetauscher ausgestaltet sein kann, wie dies durch die gestrichelten Linien angedeutet ist. Beim Umsatz von halogenierten Kohlenwasserstoffen, insbesondere von bei der Müllverbrennung entstehenden Dioxinen und Furanen, kann zusätzlich ein hier nicht dargestellter Abscheider für saure Reaktionsprodukte, wie z.B. HC1, HF, erforderlich sein.The exhaust air line 2, shown in FIG. 1, of an industrial plant (not shown further here) has an inserted catalyst 6 in the area of an expansion 4. A heat exchanger 10 and a mixing insert 12 are provided in the widening 4 in the flow direction of the exhaust air 8 upstream of the catalytic converter 6. In the direction of flow of the exhaust air 8 downstream of the catalytic converter 6, a further heat exchanger 14 is provided in the area of the widening 4, which can be configured with the heat exchanger 10 as a recuperative heat exchanger, as is indicated by the broken lines. In the conversion of halogenated hydrocarbons, in particular of dioxins and furans produced during waste incineration, a separator for acidic reaction products, such as e.g. HC1, HF, may be required.
Die in der Abluftleitung 2 strömende Abluft 8 ist mit organi- sehen Verbindungen belastet. Diese sind u.a. Alkohole, Lö¬ sungsmittel, Toluol und Xylol. Die Abluft weist vor Eintritt in die Aufweitung 4 eine Temperatur von etwa 20 °C, eine an¬ sonsten übliche LuftZusammensetzung und einen Volumenstrom von etwa 10.000 Nm3/h auf.The exhaust air 8 flowing in the exhaust air line 2 is loaded with organic compounds. These include alcohols, solvents, toluene and xylene. Before entering widening 4, the exhaust air has a temperature of approximately 20 ° C., an otherwise conventional air composition and a volume flow of approximately 10,000 Nm 3 / h.
Der Katalysator 6 besteht im Ausführungsbeispiel aus kerami¬ schen Wabenkörpern 16, wie ein solcher in Figur 2 dargestellt ist. Ein solcher Wabenkörper 16 weist üblicherweise eine Zel¬ lenanzahl von 25 bis 500 Zellen/inch2 auf. Der Wabenkörper 16 besteht im Ausführungsbeispiel aus etwa 90 Gew.-% Titandi¬ oxid, wobei das Titandioxid zu etwa 95 Gew.-% aus dem Rutil- Typ und zu etwa 5 % aus dem Anatas-Typ besteht. Der Wa¬ benkörper 16 enthält weiter etwa 3 Gew.-% Fasermaterial, z.B. Glasfasern oder Fasern aus Aluminiumoxid und/oder Siliciu- moxid, zur Erhöhung der mechanischen Festigkeit.In the exemplary embodiment, the catalyst 6 consists of ceramic honeycomb bodies 16, as is shown in FIG. 2. Such a honeycomb body 16 usually has a number of cells of 25 to 500 cells / inch 2 . In the exemplary embodiment, the honeycomb body 16 consists of approximately 90% by weight of titanium dioxide, the titanium dioxide consisting of approximately 95% by weight of the rutile type and approximately 5% of the anatase type. The honeycomb body 16 further contains about 3% by weight of fiber material, for example Glass fibers or fibers made of aluminum oxide and / or silicon oxide, to increase the mechanical strength.
Die verbleibenden sieben Gew.-% des Katalysators 6 stellen im wesentlichen die katalytisch aktiven Substanzen des Katalysa¬ tors 6 dar. Diese sind zwei Gew.-% Eisenoxid Fβ2θ3, zweiThe remaining seven% by weight of the catalyst 6 essentially represent the catalytically active substances of the catalyst 6. These are two% by weight of iron oxide Fβ2θ3, two
Gew.-% Vanadiumpendoxid V2O5 sowie jeweils ein Gew.-% Spinel¬ le der Systeme Kupfer-Mangan, Kupfer-Chrom und Mangan-Chrom mit dem zugehörigen Summenformeln CuMn2θ4, CuCr2θ4 und MnCr204.% By weight of vanadium pendoxide V2O5 and one% by weight of spinels of the copper-manganese, copper-chromium and manganese-chromium systems with the associated empirical formulas CuMn2θ4, CuCr2θ4 and MnCr 2 0 4 .
Die Abluft 8 wird mittels des Wärmetauschers 10 auf etwa 200The exhaust air 8 is increased to approximately 200 by means of the heat exchanger 10
°C aufgeheizt. Mittels des zum Wärmetauscher 10 stromabwärts gelegenen Mischeinsatzes 12 wird die Abluft 8 gemischt mit dem Ergebnis, daß eine homogene Verteilung der Temperatur der Abluft 8 über den gesamten Querschnitt der Aufweitung 4 vor¬ liegt. Durch die Kontaktierung der vorstehend genannten orga¬ nischen Verbindungen mit dem Katalysator 6 werden diese Ver¬ bindungen zu weitgehend umweltverträglichen Stoffen, z. B. Kohlendioxid und Wasser, umgewandelt.° C heated. The exhaust air 8 is mixed by means of the mixing insert 12 located downstream of the heat exchanger 10, with the result that there is a homogeneous distribution of the temperature of the exhaust air 8 over the entire cross section of the expansion 4. By contacting the above-mentioned organic compounds with the catalyst 6, these compounds become largely environmentally compatible substances, e.g. B. carbon dioxide and water.
Die aus dem Katalysator 6 austretende Abluft ist bei entspre¬ chender Dimensionierung des Katalysators 6 frei von schädli¬ chen organischen Verbindungen. Dazu sollte das Volumen des Katalysators 6 derart gewählt sein, daß der in einer Stunde durch ihn geführte Volumenstrom der Abluft 8 sein Volumen nicht um einen Faktor 50.000 überschreitet, d.h. ein Maximum von 50.000 pro Stunde für die Abluftraumgeschwindigkeit. Die Abluftraumgeschwindigkeit sollte vorzugsweise zwischen 500 und 10.000 pro Stunde liegen.The exhaust air emerging from the catalyst 6 is free of harmful organic compounds if the catalyst 6 is dimensioned accordingly. For this purpose, the volume of the catalyst 6 should be selected such that the volume flow of the exhaust air 8 passed through it in one hour does not exceed its volume by a factor of 50,000, i.e. a maximum of 50,000 per hour for the exhaust airspeed. The exhaust air velocity should preferably be between 500 and 10,000 per hour.
Mittels des Wärmetauschers 14 wird der Abluft 8 die zuvor mittels des Wärmetauschers 10 zugeführte Wärme wieder ent¬ zogen. Diese Wärme kann dem Wärmetauscher 10 wieder zugeführt werden. Alternativ kann die Abluftleitung 2 nach dem Austritt aus dem Katalysator 6 über den Wärmetauscher 10 geführt wer¬ den, wenn dieser als Rekuperativ-Wärmetauscher ausgestaltet ist.By means of the heat exchanger 14, the heat previously supplied by means of the heat exchanger 10 is extracted from the exhaust air 8 again. This heat can be returned to the heat exchanger 10 become. Alternatively, the exhaust air line 2 can be routed via the heat exchanger 10 after it has left the catalyst 6, if the latter is designed as a recuperative heat exchanger.
Bedingt durch die Wahl von Titandioxid des Rutil-Typs mit ei¬ ner spezifischen Oberfläche, auch BET-Oberfläche genannt, größer 80 m^/g, erreicht der Katalysator 6 eine besonders ho¬ he Säurebeständigkeit, Temperaturstabilität und katalytische Aktivität. Dabei wird die Säurestabilität durch die Verwen¬ dung von Titandioxid des Rutil-Typs weiter erhöht; die Tempe¬ raturstabilität wird durch den hohen Anteil an Titandioxid des Rutil-Typs erreicht. Die hohe katalytische Aktivität wird einerseits durch die Wahl der BET-Oberfläche größer 40 m2/g und andererseits durch die Wahl der katalytisch aktiven Kom¬ ponenten erzielt.Due to the selection of titanium dioxide of the rutile type with a specific surface area, also called BET surface area, greater than 80 m 2 / g, the catalyst 6 achieves a particularly high acid resistance, temperature stability and catalytic activity. The acid stability is further increased by using titanium dioxide of the rutile type; the temperature stability is achieved by the high proportion of titanium dioxide of the rutile type. The high catalytic activity is achieved on the one hand by the choice of the BET surface area greater than 40 m 2 / g and on the other hand by the choice of the catalytically active components.
In Figur 2 sind neben dem Wabenkatalysator 16 alternative Ka¬ talysatorformkörper 18 und 20 dargestellt. Diese sind Kataly- satorgranulat 18 und Katalysatorpellets 20. Das Katalysator¬ granulat 18 kann beispielsweise aus Kügelchen mit einem Durchmesser von etwa 1 bis 5 mm bestehen. Die Pellets 20 ha¬ ben üblicherweise einen Durchmesser von etwa 1 bis 5 mm und eine Länge von etwa 5 bis 30 mm. In addition to the honeycomb catalytic converter 16, FIG. 2 shows alternative shaped catalyst bodies 18 and 20. These are catalyst granules 18 and catalyst pellets 20. The catalyst granules 18 can consist, for example, of beads with a diameter of approximately 1 to 5 mm. The pellets 20 usually have a diameter of approximately 1 to 5 mm and a length of approximately 5 to 30 mm.

Claims

Patentansprüche claims
1. Katalysator (6, 16, 18, 20) zur Umsetzung von in einem Gasgemisch (8) enthaltenen organischen Verbindungen, umfas¬ send Titanoxid und mindestens eine katalytisch aktive Kompo¬ nente, d a d u r c h g e k e n n z e i c h n e t, daß Titanoxid überwiegend als Titandioxid Tiθ2 des Rutil-Typs mit einer BET-Oberfläche größer 40m2/g vorliegt.1. Catalyst (6, 16, 18, 20) for converting organic compounds contained in a gas mixture (8), comprising titanium oxide and at least one catalytically active component, characterized in that titanium oxide predominantly as titanium dioxide TiO 2 of the rutile type with a BET surface area greater than 40m2 / g.
2. Katalysator (6, 16, 18, 20) nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t, daß der Anteil an Titandioxid Tiθ2 des Anatas-Typs kleiner 25 Gew.-% ist, bezogen auf das Gesamtgewicht des eingesetzten Titanoxids.2. Catalyst (6, 16, 18, 20) according to claim 1, d a d u r c h g e k e n n z e i c h n e t that the proportion of titanium dioxide TiO 2 of the anatase type is less than 25 wt .-%, based on the total weight of the titanium oxide used.
3. Katalysator (6, 16, 18, 20) nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t, daß als kata¬ lytisch aktive Komponente zumindest eine Verbindung der Elemente Molybdän, Wolfram, Vanadium, Kupfer, Eisen, Chrom und Mangan vorgesehen ist.3. Catalyst (6, 16, 18, 20) according to claim 1 or 2, d a d u r c h g e k e n e z e i c h n e t that at least one compound of the elements molybdenum, tungsten, vanadium, copper, iron, chromium and manganese is provided as the catalytically active component.
4. Katalysator (6, 16, 18, 20) nach Anspruch 3, d a d u r c h g e k e n n z e i c h n e t, daß als kata¬ lytisch aktive Komponente zumindest eine Verbindung aus der Gruppe bestehend aus Kupfer-Mangan-Spinelle, Kupferchromite, Chromoxide, Manganchromite und Eisenoxid mit Vanadium- pentoxid vorgesehen ist.4. Catalyst (6, 16, 18, 20) according to claim 3, characterized in that at least one compound from the group consisting of copper-manganese spinels, copper chromites, chromium oxides, manganese chromites and iron oxide with vanadium pentoxide as kata¬ lytically active component is provided.
5. Katalysator (6, 16, 18, 20) nach einem der Ansprüche 1 bis 4, d a d u r c h g e k e n n z e i c h n e t, daß der5. Catalyst (6, 16, 18, 20) according to one of claims 1 to 4, d a d u r c h g e k e n n z e i c h n e t that the
Anteil der katalytisch aktiven Komponente 20 Gew.-% nicht übersteigt und vorzugsweise zwischen 2 und 10 Gew.-% liegt.The proportion of the catalytically active component does not exceed 20% by weight and is preferably between 2 and 10% by weight.
6. Katalysator (6, 16, 18, 20) nach einem der Ansprüche 1 bis 5, g e k e n n z e i c h n e t d u r c h eine Waben¬ form. 6. catalyst (6, 16, 18, 20) according to any one of claims 1 to 5, characterized by a honeycomb shape.
7. Katalysator (6, 16, 18, 20) nach einem der Ansprüche 1 bis 5, g e k e n n z e i c h n e t d u r c h eine Pellet¬ form (20) oder Granulatform (18) . 7. Catalyst (6, 16, 18, 20) according to one of claims 1 to 5, a pellet form (20) or pellet form (18).
EP96905708A 1995-03-17 1996-03-11 Process for the conversion of at least one of a COMPOUND IN A GAS MIXTURE selected from carbon monoxide and halogenated hydrocarbons Expired - Lifetime EP0814904B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19509893A DE19509893C1 (en) 1995-03-17 1995-03-17 Titanium dioxide catalyst support and its use
DE19509893 1995-03-17
PCT/DE1996/000431 WO1996029147A1 (en) 1995-03-17 1996-03-11 Catalyst for organic compounds in a gas mixture

Publications (2)

Publication Number Publication Date
EP0814904A1 true EP0814904A1 (en) 1998-01-07
EP0814904B1 EP0814904B1 (en) 2001-07-25

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JP (1) JP3920332B2 (en)
CN (1) CN1108864C (en)
AT (1) ATE203428T1 (en)
DE (2) DE19509893C1 (en)
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WO (1) WO1996029147A1 (en)

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DE19637727A1 (en) * 1996-09-16 1998-03-19 Siemens Ag Process for the catalytic combustion of a fossil fuel in an incinerator and arrangement for carrying out this process
EP2444150A1 (en) * 2010-10-22 2012-04-25 crenox GmbH Carrier catalyst consisting of pulp remnants of black solution containing titanyl sulfate

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US3948807A (en) * 1973-01-13 1976-04-06 Kuraray Co., Ltd. Oxide catalysts and process for preparation thereof
IT1197899B (en) * 1986-10-20 1988-12-21 Alusuisse Italia Spa OXIDATION CATALYST AND PROCEDURE FOR ITS PREPARATION
US4962078A (en) * 1987-05-07 1990-10-09 Exxon Research And Engineering Company Cobalt-titania catalysts, process utilizing these catalysts for the preparation of hydrocarbons from synthesis gas, and process for the preparation of said catalysts
EP0453674B1 (en) * 1987-05-07 1994-06-29 Exxon Research And Engineering Company Process for the preparation of surface impregnated dispersed cobalt metal catalysts and hydrocarbon synthesis using said catalysts
ES2081284T3 (en) * 1987-05-12 1996-03-01 Siemens Ag CATALYTIC DISPOSAL OF EXHAUST GAS AMMONIA.
DE3804722A1 (en) * 1988-02-15 1989-08-24 Siemens Ag Method, apparatus and catalyst for eliminating an organic compound from an exhaust gas
DE3913938A1 (en) * 1989-04-27 1990-10-31 Degussa PRESSLINGS BASED ON PYROGEN-PRODUCED TITANIUM DIOXIDE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE

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CN1108864C (en) 2003-05-21
CN1178483A (en) 1998-04-08
DK0814904T3 (en) 2001-11-12
WO1996029147A1 (en) 1996-09-26
DE19509893C1 (en) 1996-12-19
ATE203428T1 (en) 2001-08-15
JP3920332B2 (en) 2007-05-30
JPH11502148A (en) 1999-02-23
DE59607365D1 (en) 2001-08-30

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